DE68917939T2 - Water soluble polymers for detergent compositions. - Google Patents

Description

The present invention relates generally to water-soluble polymers, as well as to detergent compositions containing these polymers, the preparation of the polymers and to detergent compositions, and the use of the polymers. This invention relates in particular to copolymers of polymerizable, ethylenically unsaturated C3-C6 monocarboxylic acids and to copolymerizable, ethylenically unsaturated monomers containing hydrophobic groups and to polyalkyleneoxy groups, and to detergent compositions, particularly heavy-duty liquid detergent compositions for laundry and dishwashing, and the use of the copolymers in these compositions.

The use of certain polycarboxylic acid compounds, e.g. polymeric polycarboxylic acids, and their salts as additives in detergent compositions is known to enhance the effectiveness of surfactants in wetting the substrate to be cleaned. These "sequestering builders" function to form complexes with hard water ions, such as calcium and magnesium, which otherwise inactivate anionic surfactants in the detergent composition. This insoluble material tends to deposit on the fabric being washed and interferes with the uptake of optical brighteners by the fabric from the wash water, resulting in a dingy, unattractive fabric after washing. A builder, in addition to acting as a masking agent, can also help prevent soil removed by the washing process from redepositing on the fabric just washed (anti-deposit agent) and also moderates the pH (buffering agent) of the wash water. These multiple roles performed by the builder during the cleaning process make formulating a detergent composition difficult and often a matter of trial and error.

One type of polymeric polycarboxylic acid that is well known as a sequestering builder is hydrolyzed polymaleic anhydride. This type of builder is disclosed, for example, in U.S. Patents 3,308,067, 3,557,005, and 3,676,373. Maleic anhydride copolymers and derivatives are also known in the art as detergent builders. For example, U.S. Patent 3,794,605 discloses an assembled detergent composition containing a mixture of water-soluble salts of a cellulose sulfate ester and a copolymer of a vinyl compound and maleic anhydride. The builder assists in "whiteness retention" of the detergent composition by preventing redeposition of soil and deposition of hardness ion builder salts on laundered fabrics. Water-soluble salts of copolymers of a vinyl compound and maleic anhydride have also been used in detergent compositions. US Patent 3,830,745 relates, for example, to water-soluble salts of copolymers of an optionally lower alkyl-substituted cyclopentene and maleic anhydride as a builder. Other maleic anhydride copolymers which are useful as builders are, for example, those prepared with styrene (US Patent 3,676,373), with chloromaleic acid (US Patent 3,733,280), vinyl acetate or methyl methacrylate (US Patent 3,708,436), carbon monoxide (US Patent 3,761,412), tetrahydrophthalic anhydride (US Patent 3,838,113), and telomers prepared with alkyl esters or alkylene carbonates (US Patents 3,758,419 and 3,775,475) and with vinyl alcohol (US Patent 3,793,228).

In a similar vein, U.S. Patent 4,009,110 discloses terpolymers of maleic anhydride, diketene and vinyl alkyl ethers and their hydrolyzed derivatives as detergent builders and complexing agents, and the use of these terpolymers with the water-soluble salts of higher molecular weight polycarboxylic acids, such as dicarboxylic acid polymers and polymers with polymerizable monocarboxylic acids. U.S. Patent 4,554,099, which relates to an opaque liquid general purpose cleaning composition, discloses resin copolymers which are at least partially esterified with an alcohol, such as the partially esterified adducts of rosin with maleic anhydride, and copolymers of maleic anhydride with vinyl methyl ether which are partially esterified with butanol. Streak-free liquid cleaners containing similar copolymers are disclosed in U.S. Patent 4,508,635. The use of partially hydrolyzed polymaleic anhydride as a component in a detergent composition adapted for washing fabrics after they have been dyed is disclosed in U.S. Patent 4,545,919.

U.S. Patent 4,471,100 discloses copolymers of maleic acid salts and polyalkylene glycol monoallyl ether for use as dispersants in, inter alia, cement and mortar. The specification of British Patent No. 1,167,524 discloses similar copolymers except that the polyalkylene glycol chain is capped with a monovalent aliphatic, cycloaliphatic, arylaliphatic, aryl-alkylaryl or acyl group having at least four carbon atoms and that the polymerizable "surfactant monomer" or "surface active monomer" can be derived from ethylenically unsaturated mono- or dicarboxylic acids as well as from allyl functional compounds.

Another invention in this tradition is that of U.S. Patent 4,559,159 ("'159 Patent"), which discloses copolymers of ethylenically unsaturated monocarboxylic acids and dicarboxylic acids (and their anhydrides such as maleic anhydride) partially esterified with an alkoxylated (C1-C18) alkylphenol. These copolymers are used as "detergent adjuvants" to replace conventional detergent builders such as polycarboxylic acids. These adjuvants simultaneously optimize the primary and secondary detergency of the detergent in the composition.

The use of maleic anhydride in the '159 patent appears to be motivated by the stated simplicity of preparing maleic anhydride copolymers, as these copolymers can be prepared by first simply copolymerizing the acid monomers in an aqueous solution and then partially esterifying the intermediate polymer by reacting the alkoxylated alkylphenol with maleic anhydride to form the monoester (column 5, lines 54-64). In addition, a neutralization step can be avoided by using a mixture of the soluble salt of the dicarboxylic acid and a monocarboxylic acid or a mixture of the soluble salt of a monocarboxylic acid and the dicarboxylic acid (column 8, lines 53-65). The '159 patent mentions an advance over the prior art which employed maleic anhydride"acrylic acid copolymers and methyl vinyl ether/maleic anhydride copolymers (items 4 and 5 in the table in column 16).

Another general type of polymeric polycarboxylic acid builder is polyacrylic acid. For example, U.S. Patent 3,706,672 discloses sodium polyacrylate as a replacement for a polyphosphate builder in household detergent compositions. A polyacrylic acid with high chelating value is disclosed in U.S. Patent 3,904,685. The use of oligomeric poly(alkyl)acrylic acids (molecular weight 500-10,000) and their salts as biodegradable builders for detergent compositions is disclosed in U.S. Patent 3,922,230. Similarly, U.S. Patent 3,950,260 relates to water-soluble homopolymers of acrylic acid and methacrylic acid and their salts as builders, with the preferred degree of polymerization being fixed by a viscosity criterion. It is disclosed in U.S. Patent 3,566,504 that crosslinked homopolymers of acrylic acid are suitable "structurants" for highly alkaline liquid detergent compositions.

Copolymers of acrylic acid and other monomers are also known as builders. For example, copolymers of acrolein and acrylic acid are disclosed as builders in U.S. Patents 3,853,781 and 3,896,086. Similar polymers are disclosed in U.S. Patent 4,031,022, which relates to copolymers of acrylic acid and alpha-hydroxyacrylic acid and their water-soluble salts and use as detergent builders. These copolymers can suspend lime (calcium carbonate) to an extent that far exceeds their stoichiometric capacity. U.S. Patent 3,920,570 describes a method for sequestering ions by using a water-soluble salt of a poly-alpha-hydroxyacrylic acid as a sequestering polyelectrolyte. Salts of terpolymers derived from an alkyl alcohol, sulfur dioxide and acrylic or methacrylic acid are disclosed in U.S. Patent 3,883,446 as a replacement for phosphorus-containing builders. U.S. Patent 3,719,647 discloses copolymers of (meth)acrylic acid and polyethoxylated (meth)acrylic acid as "whiteness maintenance" agents in conventional tripolyphosphate-built granular detergents. These copolymers preferably have a molecular weight between 30,000 and 200,000.

The use of mixtures of polyacrylic acid and other polymers in detergent compositions is also known. For example, the use of mixtures of polyacrylic acid and another polymer, poly(N,N-dicarboxymethacrylamide), as builders is disclosed in U.S. Patent 3,692,704. Similarly, the use of mixtures of polyethylene glycol and polyacrylate in detergent compositions to improve the removal of clay soils is disclosed in U.S. Patent 4,490,271. The mixture is preferably used at relatively low levels and a non-phosphorous detergent builder must also be included in these solid detergent compositions.

US Patent 4,571,303 discloses the use of water-soluble polyacrylates to improve the storage stability of polyethylene terephthalate-polyoxyethylene terephthalate copolymers, which allow the release of soil in particulate, non-ionic detergent compositions.

EP-A-0 147 745 discloses copolymers of acrylamide alkanesulfonic acid and copolymerizable, ethylenically unsaturated esters of hydrocarboxypoly(alkenoxy)alkanol with acrylic and methacrylic acid as lime soap dispersants.

Despite the considerable advances made in the cleaning art in reducing the amount of water eutrophicating phosphate builder in detergent compositions and in reducing the redeposition of soil and masking hard water ions (lime soap dispersibility) during the washing process by using water soluble polyions, there remains a considerable need for further improvement, particularly in liquid cleaning compositions. The need is particularly acute when detergent compositions are used in washing fabrics which are all cotton and are particularly sensitive to redeposition of soil during the cleaning process. Recently, clothing made entirely of cotton and other natural fabrics has become increasingly popular.

Modern liquid laundry detergents for home laundry are complex, highly engineered products. See, for example, S.C. Stinson, Chemical and Engineering News, January 26, 1987, pages 21-46 and U.S. Patent 4,507,219 (a high performance liquid detergent composition containing eleven components). The formulation of liquid laundry detergent compositions is a highly unpredictable process, given the complex variety of interactions possible between the many components of these products and the critical importance of surface phenomena in the cleaning process. There is a need for a product which can serve as both an anti-scaling agent in lime soap dispersants and which is not only compatible with the highly complex liquid detergent compositions currently sold to the consumer, but which also works without reducing other important performance characteristics of the detergent compositions.

DESCRIPTION OF THE INVENTION

The present invention provides water-soluble polymers and dispersants and detergent compositions containing them, and a process for preparing a class of these polymers. The water-soluble polymers are useful as additives in detergent compositions in which they serve as builders, lime soap dispersants by sequestering "hard water" cations (e.g., Ca++), and as soil antiflocculating agents (agents to prevent redeposition). The water-soluble polymers are of particular interest in liquid detergent compositions such as commercial liquid household laundry detergent compositions (heavy duty liquid detergents) and liquid dishwashing products (light duty liquid detergents). In high performance liquid detergent compositions, the polymers of the present invention provide a significant enhancement of the ability of the detergent composition to resist redeposition of particulate soil, particularly when cotton fabric is washed. This enhancement is achieved in a water hardness range (20-120 ppm Ca⁺⁺, 50-300 ppm as CaCO₃). In addition, the removal of oily dirt (such as sebum from sweat) is also enhanced.

It is particularly significant that these enhancements in the performance properties of important detergent compositions are achieved without correspondingly significant deterioration of other properties. When compared to commercial detergent controls which do not contain the polymers of the present invention, liquid detergent compositions of this invention retain the ability to effectively remove particulate soils and the ability to prevent redeposition of oily soils. Furthermore, the polymers, when added in effective amounts, are compatible with commercial heavy-duty liquid detergent compositions. Unlike phosphate builders, the polymers of the present invention do not adversely affect the activity of enzymes in liquid detergent compositions, opening the door to enzyme-containing liquid detergent products.

The water-soluble polymers of the present invention include two broad structural classes. The polymers in these classes share several important characteristics. First, both groups of polymers are prepared from a monomer, e.g., polymerizable, ethylenically unsaturated C3-C6 monocarboxylic acids and their salts, such as acrylic acid and sodium acrylate. Second, the polymers must contain a "surfactant" radical or "surface-active" moiety containing a hydrophobic group, e.g., a (C1-C18) hydrocarbyl group, which moiety is attached to a polyalkyleneoxy group. Depending on the manufacturing process used, this residue may comprise a portion of a polymerizable, ethylenically unsaturated "surfactant monomer" or "surface active monomer" copolymerized with the acid and/or acid salt comonomer, or the residue may comprise a portion of an alcohol used to esterify or transesterify a polymer, e.g., carboxylic acid and/or carboxylic acid ester residues. As a third alternative, the residue may comprise a portion of a mercaptan-functional chain transfer agent used in polymerizing a monomer, e.g., an ethylenically unsaturated C3-C6 carboxylic acid and/or salts of such a monomer. The water-soluble copolymers of the present invention are structurally different from those disclosed, for example, in U.S. Patent 4,559,159 in that the polymerizable ethylenically unsaturated dicarboxylic acids and their respective salts and anhydrides are excluded from the monomer compositions which are polymerized to produce the water-soluble polymers of this invention. They are functionally distinguished by, inter alia, their superior performance in liquid detergent compositions.

In addition to the residues of polymerizable ethylenically unsaturated monocarboxylic acids and surfactant residues, the water-soluble polymers of the present invention may comprise residues of "carboxylate-free" monomers. By "carboxylate-free" monomer is meant an ethylenically unsaturated copolymerizable monomer which does not include pendant carboxylic acid and/or carboxylate salt functionality. An example of a presently preferred carboxylate-free monomer is ethyl acrylate. Typically, the carboxylate-free monomer is monocarboxylic acid and/or the monocarboxylic acid salt monomer. A "carboxylate-free" monomer may contain a surfactant moiety, as in the case of an allyl ether functional surfactant monomer.

The water-soluble polymers of the first structural class of this invention share a common structural feature. The surfactant radical or moiety can be positioned on either side along the "backbone" of the polymer chain, with the "backbone" being considered to be made up of a sequence of alkyl groups which may have pendant carbonyl groups. The surfactant moieties are thus covalently linked to one or more sites along the interior of the polymer chain. As discussed below, a number of different methods can be used to prepare the water-soluble polymers of this class.

Water-soluble polymers in the second structural class of polymers of the present invention must have a surfactant moiety at one end of the polymer chain. Polymers in this structural class are typically prepared by incorporating a chain transfer agent containing the surfactant moiety into the polymerization reaction mixture. Polymerization of individual polymer molecules is terminated by the chain transfer agent. The chain transfer process results in a surfactant moiety covalently linked to the end of the polymer chain.

The water-soluble polymers of the first class can be described with the general formula:

A(B)m(C')n(D)oE (I)

it being understood that the groups or residues B, C' and D can be arranged in any order within a given polymer molecule. The end group A is selected from Rb-C(O)-Ra- and RcC(O)NH-Rd-. However, it is contemplated that depending on the polymerization process and initiator system used, the group A may contain a fragment of the initiator or another element of the initiator system. Ra is a (C1-C5)alkylidene group, e.g. a (C2-C5)alkylidene group. A may be, for example, ethylidene or propylidene.

Rc is a group having the formula R¹Z(X¹)a(X²)b-. This "surfactant moiety", like surfactants, contains both a hydrophobic portion and a hydrophilic portion. The hydrophobic portion R¹ is a hydrocarbyl group selected from (C₁-C₁₈)alkyl, alkaryl in which the alkyl portion contains 1 to 18 carbon atoms, and aralkyl in which the alkyl portion contains 1 to 18 carbon atoms.

Preferably, R¹ is a (C₁-C₁₈)hydrocarbyl group selected from (C₁-C₁₈)alkyl, (C₇-C₁₈)alkaryl and (C₇-C₁₈)aralkyl. Examples of such alkyl groups are methyl, t-butyl, n-octyl, hexadecyl and octadecyl. Examples of such alkaryl groups are octylphenyl, nonylphenyl and tolyl. An example of such an aralkyl group is benzyl. Z is a group which connects the hydrophobic and hydrophilic portions of the surfactant moiety Rc and is selected from -O-, -S-, -CO₂-, -CONR²- and -NR²-. More preferably, Z is -O-. R² is selected from H, (C₁-C₄)alkyl and H(X¹)d(X²)e-, where d and e are independently 0 or a positive integer and the sum of d and e is 1 to 100 In one embodiment, the polymer contains Rc groups having the formula R'O(YX')a-, wherein R' is (C1-C18)alkyl, preferably (C10-C18)alkyl and a is from 5 to 45. The hydrophilic portion may also be poly(alkyleneoxy) wherein the alkyl portion is selected from propylene and higher alkylene.

The hydrophilic portion of the surfactant moiety is, for example, a poly(alkyleneoxy) chain, (X¹)a(X²)b, where X¹ is -CH₂CH₂O- (ethyleneoxy) and X² is an alkyleneoxy other than ethyleneoxy and preferably -C(CH₃)HCH₂O- (propyleneoxy). Here, a is a positive integer and b is 0 or a positive integer and is the sum of a and b from 3 to 100. It is contemplated that the initiators X¹ and X² may be arranged in any sequence. The sequence may, for example, reflect the statistics of the copolymerization of a mixture of ethylene oxide and propylene oxide. Alternatively, the ethyleneoxy unit and the propyleneoxy units can be arranged in blocks, representing, for example, a sequential homopolymerization of ethylene oxide and propylene oxide.

Rb is a group -OQ or Rc, the latter being defined above. Q is selected from H and the positive ions which form soluble salts with carboxylate anions. Q can be, for example, an alkali metal ion such as Na+ or K+, or ammonium or a tetraalkylammonium such as tetramethylammonium. The pH of the polymerization medium can be adjusted by adding an alkali metal base such as sodium or potassium hydroxide. The strong base reacts with carboxylic acid to form an alkali metal carboxylic acid salt.

Rd is a group containing a carbon-carbon monovalent formed during polymerization of the polymer from a polymerizable carbon-carbon doubly formed. Preferably, Rd is the residue of a polymerizable, ethylenically unsaturated compound, e.g., a urethane group. The surface-active residue Rc is bonded to the group Rd via the carbamate group, it being understood that this carbamate group contains the terminal oxygen atom of the alkylene oxide chain.

The structure of group A may depend on the nature of the initiation of vinyl addition to the polymer chain by means of free radicals. In general, group A and group E may contain a fragment of a polymerization initiator or a chain transfer agent. The nature of these fragments or end groups is well known in the art of polymerizations. A variety of end groups may be introduced by different polymerization processes and these end groups may contain, for example, sulfur. These polymerization processes are well known. For example, by polymerization processes with mercaptan chain transfer agents, A may contain the following:

Alkyl or aryl sulfide (introduced by using alkyl or aryl mercaptans), carboxylic acid functional sulfides (introduced by using mercaptocarboxylic acids), ester sulfides (introduced by using mercaptocarboxylate ester compounds). Oxidation of the above-described sulfide end groups after polymerization can result in sulfoxide and/or sulfone end groups. If an alcohol such as isopropanol or benzyl alcohol is used as a chain transfer agent, end groups containing alcohols or lactones can result. In addition, a chain transfer solvent such as cumene can be used with a retained alkyl aromatic end group. Control of molecular weight using various initiators in the absence of a chain transfer solvent can result in a variety of A groups. For example, if perphosphates or persulfates are used, phosphate or sulfate end groups can result. If hydrogen peroxide is used, the end groups obtained are hydroxyl. Use of t-butyl perester will result in ether or alkane end groups.

In summary, the terminal group A is either a group with a single pendant carboxylic acid or carboxylic acid salt, or a pendant surfactant residue that is attached to the backbone of the polymer chain via an ester or a carbamate group.

B is a group with the formula -Re-C(O)-OQ, where Re is a trivalent saturated aliphatic radical with chains of two to five carbons. Examples of Re radicals are

-CH(CH3)-

and

The group B is therefore a residue of an ethylenically unsaturated C₃-C₆-monocarboxylic acid or its water-soluble salt.

C' is a group consisting of

and

is selected. The group C' is, for example, a pendant surfactant moiety Rc which is connected to the interior of the polymer chain via an ester group, a carbamate linkage, a urethane group or the like. Alternatively, the surfactant moiety can be connected to the "backbone" of the polymer chain via carbon-carbon bonds if the group C' is derived from polymerization of an allyl or vinyl functional surfactant monomer. Here, Rf is a trivalent saturated aliphatic group containing a carbon-carbon single bond formed during polymerization of the polymer from a polymerizable carbon-carbon double bond. Preferably, Rf, like Rd, is derived from polymerization of an ethylenically unsaturated carbamate functional monomer.

D is a group having the formula -Re-G, where G is an organic group not containing -CO₂Q or Rc. D is thus the residue of a "carboxylate-free", ethylenically unsaturated polymerizable monomer such as ethyl acrylate or methyl methacrylate. In one embodiment, G is selected from -NH₂, -NHR3, -OR3, -OR⁴-OH, -OR⁴-NH, -OR⁴-SO₃Q, -OR⁴-PO₃Q, where R3 is (C₁-C₈)alkyl and R⁴ is (C₁-C₈)alkylene.

E is preferably a divalent saturated aliphatic radical having chains of two to five carbon atoms, that is, a group selected from Rc-Rg, Rb-C(O)-Rg and Rc-C(O)NH-Rd, where Rg is a (C1-C5)alkylene, e.g. a (C2-C5)alkylene. E thus represents the group at the end of the polymer chain at which the polymerization was terminated. Examples of radicals Rg are, for example, -CH2- CH2-, -CH(CH3)-CH2-, -CH(C2H5)-CH2- and -CH2-CH(CH3)-. The group E can also contain radicals associated with the chain termination step, such as, for example, -CH2-CH2-CH2-, -CH(CH3)-CH2-, -CH(CH2H5)-CH2- and -CH2-CH(CH3)-. B. Fragments of chain transfer agents.

In the general formula of this first class of water-soluble polymers, m is a positive integer and n and o are independently 0 or a positive integer. The value of m is chosen such that the residue of the ethylenically unsaturated C₃-C₈ monocarboxylic acid and/or the water-soluble salts of such acids, (Bm), comprises 20-95 weight percent of the polymer. The value of n is chosen such that the surface-active residue, Rc, comprises from 80 to 4 weight percent of the polymer. The value of o is chosen such that the residue of the carboxylate-free monomer, (D)o, comprises from 0 to 30 weight percent. of the polymer. The sum of the weight percentages of A, (B)m, (C)n, (D)o is 100%. The polymer has a number average molecular weight of 500 to 50,000.

An example of a polymer represented by formula (I) is the polymer with the structural formula:

in which A, which Rb-C(O)-Ra should be chosen,

where Ra is ethylidene, ie

and Rb is -OQ; similarly B, which is

should be elected,

where Re is "ethenyl", ie

is; additionally C', which is

should be elected,

where Re is "ethenyl", ie

is;

where Rc

wherein R¹ is nonylphenyl, Z is O,

X¹ is (CH₂CH₂O) and a is 30;

finally E, which is to be chosen as Rb-C(O=Rg-, is -(CH₂-CH₂-CO₂Q), Rg is ethylene, i.e. -CH₂-CH₂-, and Rb is -OQ. In this example, the sixty B units and the twenty-five C' units are randomly distributed in the chain.

A second example of a polymer represented by formula (I) is the polymer with the structural formula:

Here A, B and E are as above in the first polymer and is C', which is

should be elected,

where Rf

is; X¹ is CH₂CH₂O; Z is S; and R¹ is C₄H�9;

and D, soft as

should be elected,

is; wherein

and G is OC₂H₅, ethoxy. In this second example, the fifty B units, the ten C units, and the six D units are randomly distributed in the polymer chain, with the distribution being controlled by the ratios of the monomer reactivities.

A third example of a polymer represented by formula (I) is the polymer with the structural formula:

wherein: EO = ethylene oxide, and (C₁₆-C₁₈) = a (C₁₆-C₁₈)alkyl group or an alkaryl or aralkyl group in which the alkyl part contains 16-18 carbon atoms.

The second class of polymers of the present invention are terminated by surface active moieties and can be represented by the formula L-J. L in this formula is a group having the formula Rc-C(O)(CHR3)c-S-, where Rc is as defined above, R3 is selected from H, CH3- and C2H5, and the index c is 1, 2 or 3.

The group -J in this formula has the formula (B)m(D)oE, where B, D, E, m and o are given above. In one embodiment, the sum of m and o is from 20 to 150. The weight ratio of L to J is from 1:340 to 7:1, with 1:100 to 2:1 being preferred, 1:50 to 1:1 being more preferred, and 1:10 to 1:2 being especially preferred.

The polymers of the present invention may, for example, have a number average molecular weight of from 1,000 to 15,000, preferably from 1,000 to 5,000. The polymers of the first class may, for example, be polymers comprising one or more of: (a) units of an acrylic and/or methacrylic acid ester of an alkylpolyalkylene oxide; (b) units of an acrylic and/or methacrylic acid ester of an alkylpolyalkylene oxide of urethanes; and (c) alkylpolyalkylene oxide thio end groups.

The polymers of the first class of the present invention can be prepared by a variety of processes, for example by conventional vinyl polymerization processes in aqueous solution.

A particularly preferred process for preparing polymers of the first class is disclosed in EP-A-03 24 569 filed on the same date as the present application. In this "in-process functionalization" process, a surfactant group-containing compound, in particular a surfactant alcohol having the structure R¹Z(X¹)a-(X²)bH, is used as the solvent or medium for the polymerization of the ethylenically unsaturated C₃-C₆ monocarboxylic acid monomer and optionally carboxylate-free monomers. After polymerization, the mixture of polymer and surfactant alcohol is heated to complete esterification. The water of condensation is removed from the reaction mixture by vacuum distillation or by azeotropic distillation. If azeotropic distillation is used, a solvent such as e.g. B. toluene, either before or after the polymerization step. If desired, a chain transfer agent, preferably a mercaptan, is added during the polymerization to control the molecular weight of the polymer.

The water-soluble polymers of the first class of the present invention can be prepared by any conventional polymerization technique, such as solution polymerization. These polymers can be prepared, for example, by polymerizing monomers dissolved in an aqueous solvent. Both batch processes and continuous processes can be used. Of the batch processes, both single shot and multiple shot can be used as a gradual addition method.

Conventional means for initiating the polymerization of ethylenically unsaturated monomers can be used, e.g. both thermal and redox initiation systems. Water-soluble initiators are preferred. In addition, conventional means for Controlling the average molecular weight of the polymer, such as by the inclusion of chain transfer agents in the polymerization reaction mixture, may be used. Examples of chain transfer agents which may be used include mercaptans, polymercaptans and polyhalogen compounds. In particular, chain transfer agents such as long chain alkyl mercaptans such as n-dodecyl mercaptan; alcohols such as isopropanol and isobutanol; and halogens such as carbon tetrachloride, tetrachloroethylene and trichlorobromoethane may be used. Typically, from 0 to 20 wt.%, based on the weight of the monomer mixture employed and depending on the polymer molecular weight desired, may be used. However, if the solvent also acts as a chain transfer agent, as in the case of alcohols such as isopropanol and isobutanol, the chain transfer agents may be increased in amount. B. isopropanol, a substantially greater proportion of the solvent chain transfer agent can be used (for example, more than 100% based on the weight of the monomer mixture). The amount of chain transfer agent used is selected to provide a number average polymer molecular weight of from 500 to 50,000, and preferably from 1,000 to 15,000.

Examples of polymerization initiators that can be used to prepare polymers in both structural classes include free radical type initiators such as ammonium and potassium persulfate, which are used alone (thermal initiator) or as the oxidizing component of a redox system that also contains a reducing component such as potassium metabisulfite, sodium thiosulfate or formaldehyde sodium sulfoxylate. Examples of free radical peroxide initiators include the alkali metal perborates, hydrogen peroxide, organic hydroperoxides and peresters. In a redox system, the reducing component is often referred to as the accelerator. The initiator and accelerator, commonly referred to as the catalyst, catalyst system or redox system, can be used in an amount of from 0.001% to 5% each, based on the weight of the monomers to be copolymerized. Examples of redox catalyst systems include tert-butyl hydroperoxide/formaldehyde sodium sulfoxylate/Fe(II) and ammonium persulfate/sodium bisulfite/sodium hydrogen sulfite/Fe(II). Activators such as the chloride or sulfate salts of cobalt, iron, nickel or copper can be used in small amounts. Examples of thermal initiators include: tert-butyl peroxypivalate, dilauryl peroxide, dibenzoyl peroxide, 2,2-azobis(isobutyronitrile), dicumyl peroxide, tert-butyl perbenzoate and ditert-butyl peroxide. The polymerization temperature can be from ambient temperature to the reflux temperature of the polymerization reaction mixture. Preferably, the polymerization temperature is optimized for the catalyst system used, as is customary. The polymerization may be carried out at atmospheric pressure, preferably when the reaction vessel is sparged or purged with an inert gas such as nitrogen to reduce oxygen inhibition of the reaction. Alternatively, either subatmospheric or superatmospheric pressure may be used in the reaction conditions.

The average molecular weight of the polymers can be controlled by employing a water-miscible liquid such as an organic compound which acts as a chain transfer agent, such as a lower alkyl alcohol, with isopropanol being particularly preferred. In this particularly preferred method of preparing the polymers of the present invention, the dielectric constant of the non-aqueous solvent must be sufficiently high so that the solvent can dissolve ethylenically unsaturated C3-C6 monocarboxylic acid monomers or their water-soluble salts. A mixed solvent, e.g., water and a water-miscible organic solvent, may also be used. Mixed solvents containing both water and isopropanol are preferred. However, other organic compounds which are miscible with water at the polymerization temperature, such as ethanol, carbitols, alkyl cellosolves (trademark of DuPont de Nemours), and glymes, may also be used.

The polymers of the first class contain 20 to 95% by weight of the polymer of residues of an ethylenically unsaturated monocarboxylic acid having preferably 3 to 5 carbon atoms or the water-soluble salt of such an acid. The residues carrying the acid and/or the acid salt preferably originate from the polymerization of ethylenically unsaturated C3-C6 monocarboxylic acids and/or their water-soluble salts. Alternatively, the residues carrying the carboxylic acid are derived from the hydrolysis of an ester precursor, the residue carrying the ester precursor having been formed by the polymerization of a polymerizable, ethylenically unsaturated carboxylic acid ester whose acyl moiety contains 3 to 6 carbon atoms.

The polymerization reaction mixture may contain either a single species of an ethylenically unsaturated C3-C6 monocarboxylic acid or a salt of such an acid which is soluble in the polymerization solvent, or a mixture of the acid and the salt of the acid. Alternatively, the polymerization mixture may contain a mixture of two or more ethylenically unsaturated C3-C6 monocarboxylic acids and/or soluble salts of such acids.

When a solution polymerization process is used, it is preferred that the salt also be soluble in the polymerization solvent if the solvent is not water. When water or a solvent with a high dielectric constant is used, it is preferred to add monomer to the polymerization reaction mixture gradually. Additional components, such as initiator, may be included with the added monomer. The composition of this monomer feed may vary over time. While the initial feed may contain a single ethylenically unsaturated C3-C6 monocarboxylic acid monomer or a soluble salt of such monomer, the subsequent monomer feed may contain a second such ethylenically unsaturated C3-C6 monocarboxylic acid monomer or a mixture of such monomers.

Examples of ethylenically unsaturated C3-C6 monoacid monomers which can be used include acrylic acid, methacrylic acid, beta-acryloxypropionic acid, vinylacetic acid, vinylpropionic acid and crotonic acid. Acrylic and methacrylic acid are preferred, and acrylic acid is particularly preferred. Examples of polymerizable ethylenically unsaturated C3-C6 monocarboxylic soluble salts include sodium acrylate, potassium methacrylate, sodium acryloxypropionate, ammonium propionate and tetramethylammonium acrylate. Sodium and potassium salts of acrylic and methacrylic acid are preferred; and sodium acrylate is particularly preferred.

In one group of processes for preparing the polymers of the first class of the present invention, the monomer carrying the carboxylic acid and/or acid salt is treated with a "surfactant Monomer", e.g. the surfactant moiety Rc. The surfactant monomer can be prepared by esterification of a copolymerizable, ethylenically unsaturated carboxylic acid compound. Examples of ethylenically unsaturated carboxylic acid compounds which can be so esterified include ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid. Alternatively, an ethylenically unsaturated carboxylic acid ester can be transesterified to produce the surfactant monomer. Examples of ethylenically unsaturated carboxylic esters which can be transesterified include ethyl acrylate and methyl methacrylate. Conventional esterification and transesterification processes and conditions can be used. Acidic esterification catalysts can be used, such as p-toluenesulfonic acid, methanesulfonic acid, acidic organometallic salts and acidic ion exchange resins.

Polymers of the first class can be prepared by copolymerizing an ethylenically unsaturated C3-C6 carboxylic acid monomer with a surface-active monomer, as disclosed in DE-A-27 58 122.

In general, the surface-active monomer can be any ethylenically unsaturated compound, including the surface-active moiety Rc, which can lead to a water-soluble polymer of the first classes as claimed and which is copolymerizable with the ethylenically unsaturated C3-C6 monocarboxylic acid and/or the water-soluble acid salt. The surface-active monomer can, for example, be a surface-active moiety which is covalently bonded via a carbamate functional group to a part of the compound which contains a copolymerizable carbon-carbon double bond. After polymerization, this carbon-carbon double bond becomes a carbon-carbon single bond. Examples of this type of surface-active monomer are, for example, B. the carbamate, which is formed by the reaction of ethylenically unsaturated isocyanates and alcohols containing the surface-active radical. Examples of such monomers are in particular the carbamate, which is formed with a surface-active alcohol and an alpha,alpha- dimethyl-meta-isopropenylbenzyl isocyanate, and the carbamate, which is formed by the reaction between a surface-active alcohol and isocyanoethyl methacrylate.

Other examples of surface-active monomers are, for example, allyl, methallyl and vinyl functional surface-active monomers. (Meth)allyl surface-active monomers can be represented by the formula CH₂=CR¹CH₂Rc, where R¹ = H, CH₃; and the vinyl surface-active monomers by the formula CH₂=CH-Rc. Examples of (meth)allyl surface-active monomers are, for example, allyl ethers, such as. B. CH₂=CH-CH₂O-(CH₂CH₂O)₂₀-C₈H₁₇ and CH₂=CH-CH₂O- (CH₂CH₂O)₂₅-C₆H₄-C₉H₁₇. Examples of surface-active vinyl-functional monomers are e.g. CH₂=CH-O-(CH₂CH₂O)₁₈C₃H�7 and CH₂=CH-S-(CH₂CH₂O)₁₉-C₆H₄-C₈H₁₇. The surfactant (meth)allyl functional monomers can be prepared by the methods disclosed in British Patent Specification No. 1,273,552.

A surface-active monomer can generally be prepared by reaction between a first compound containing a polymerizable ethylenic unsaturation and a second reactive functional group and a second compound containing the surface-active moiety and a functional group which reacts with the second functional group on the first compound. The preparation of suitable surfactant monomers is disclosed, for example, in British Patent Specification No. 1,167,534 and in U.S. Patent Nos. 4,138,381 and 4,268,641. The surfactant moiety-containing compound is preferably an alcohol in which the reactive functional group is the hydroxyl group. Generally, the surfactant moiety-containing group is itself a surfactant group since it must contain both a hydrophobic hydrocarbyl group and a hydrophilic poly(alkyleneoxy) group. It should be noted, however, that because the hydrocarbyl group is as small as C₁ (ie, methyl) and the poly(alkyleneoxy) group may contain as many as 100 ethylene oxide units, the compound containing the surfactant moiety itself need not be functional as a surfactant.

Preferably, the surfactant group-containing compound is prepared by a conventional process in which a hydrocarbyl alcohol, such as a (C1-C18)alkanol or a (C1-C12)alkylphenol, is treated with an alkylene oxide, preferably ethylene oxide, to form a hydrocarboxypoly(alkyleneoxy)alkanol, preferably a (C1-C1)alkaryloxypoly(alkyleneoxy)ethanol. For example, a nonylphenoxypoly(ethyleneoxy)ethanol, such as Triton (trademark of Rohm and Haas Company) N-57, N-101, N-111 or N-401, may be used. Similarly, octylphenoxypoly(ethyleneoxy)ethanols, such as Triton (trademark of Rohm and Haas Company) N-57, N-101, N-111 or N-401, may be used. B. Triton X-15, X-35, X-45, X-100, X-102, X-155, X-305 and X-405 can be used. In addition, straight-chain polyethoxylated alcohols can also be used. For example, a polyethyleneoxylated lauryl alcohol, a polyethyleneoxylated oleyl alcohol and a polyethyleneoxylated stearyl alcohol, such as those sold under the trademark Macol, can be used.

As an alternative to copolymerizing one or more ethylenically unsaturated C3-C6 monocarboxylic acid monomers and/or soluble salts of the monomers with one or more surfactant monomers, the surfactant moiety-containing compound can be used to partially esterify or transesterify a polymer formed by polymerizing the one or more ethylenically unsaturated C3-C6 monocarboxylic acid monomers and/or the water-soluble salt of such monomer. The esterification of such polymeric polycarboxylic acids is well known and conventional methods can be used to effect the esterification. For example, the polymers of the first class can be prepared by transesterification of homopolymers of monoethylenically unsaturated C3-C6 carboxylic acids or copolymers thereof with an alcohol containing the surface-active radical, as disclosed, for example, in EP-A-0 134 995. The esterification of polyacrylic acids is well known in the polymer art.

In this case, a surfactant monomer does not need to be prepared and isolated. The use of this process may therefore be preferred over a process in which the surfactant monomer is prepared and reacted with the acid monomer. The factors that may influence the choice of a process are, for example, the relevant difficulty of preparing and purifying or isolating a particular surfactant monomer, the reactivity ratio of the surface-active monomer with the acid monomer or monomers to be used in the polymerization and the effectiveness of the esterification process.

If desired, small amounts of additives such as surfactants and miscible cosolvents may be used in the polymerization medium. Small amounts of surfactants may be added to the monomer solution to improve monomer compatibility, particularly when both a hydrophilic and a hydrophobic monomer are used, to reduce coagulation and improve the application properties of the polymer composition. When an aqueous or hydrophilic polymerization medium is used, anionic surfactants such as alkyl sulfates, alkylaryl sulfonates, fatty acid soaps, monoglyceride sulfates, sulfoether esters, and sulfoether N-alkylamides of fatty acids may be used. Similarly, nonionic surfactants such as alkyl sulfates, alkylaryl sulfonates, fatty acid soaps, monoglyceride sulfates, sulfoether esters, and sulfoether N-alkylamides of fatty acids may often be used. B. Poly(alkyleneoxy)alkanols of alkylphenols and alkyl ethers, and poly(alkyleneoxy) derivatives of aliphatic alcohols and other hydroxy compounds, carboxyl compounds and carboxamides and sulfonamides. A preferred surfactant is Triton (a trademark of Rohm and Haas Co.) X-100, i.e. octylphenoxypoly(ethyleneoxy)ethanol. The amount of surfactant employed depends on the type of surfactant used and on the end use for which the polymer composition is intended and can vary from 0 to 10% by weight of monomer.

Of the monomers which may optionally be included in the polymerization mixture to prepare the polymers of the present invention are the "carboxylate-free" monomers. This class of monomer is broadly defined to include all copolymerizable, ethylenically unsaturated monomers, excluding the carboxylic acid monomers and the surfactant monomers. The carboxylate-free monomers are therefore, for example, ethylenically unsaturated, polymerizable monomers containing carboxyl ester functional groups, such as the lower alkyl acrylates; it should be understood that the carboxylate-free monomer in any case does not fall into the class of surfactant monomers.

Examples of carboxylate-free, ethylenically unsaturated monomers include: (meth)acrylamide and substituted (meth)acrylamides, such as N,N-diethylacrylamide; N-ethylacrylamide and N,N-dipropylmethacrylamide; alkyl (meth)acrylates, such as. B. Methyl methacrylate, ethyl acrylate, methyl acrylate, n-butyl acrylate, cyclohexyl acrylate, isopropyl acrylate, isobutyl acrylate, n-amyl acrylate, n-propyl acrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, neopentyl acrylate, n-tetradecyl acrylate, n-tetradecyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, isoamyl methacrylate, cyclopentyl methacrylate, n-decyl methacrylate, 2-ethylhexyl acrylate and lauryl acrylate, hydroxy substituted (meth)acrylates, such as. B.. 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate, amino-substituted alkyl (meth)acrylates, e.g. mono- and dialkylammoalkyl (meth)acrylate, such as dimethylaminooctyl methacrylate, methylammocthyl methacrylate and 3-aminopropyl acrylate, other acrylate and methacrylate esters, such as methyl-2-cyanoacrylate, 2-bromoethyl methacrylate, isobornyl methacrylate, phenyl methacrylate, 1-naphthyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypropyl methacrylate, benzyl methacrylate, 2- Phenylethylene methacrylate, 3-methoxybutyl acrylate, 2-methoxybutyl methacrylate and 2-n-butoxyethyl methacrylate; vinyl esters such as vinyl versatate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl 2-ethylhexanoate and vinyl decanoate; esters of other ethylenically unsaturated carboxylic acids such as monoalkyl, dialkyl and trialkyl esters of di- and tricarboxylic acids such as itaconic acid such as di(2-ethylhexyl)maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconate, trimethyl aconitate, diethyl mesaconate, monomethyl itaconate, mono-n-butyl itaconate; di(2-ethylhexyl)itaconate and di(2-chloroethyl)itaconate; sulfonic acids such as B. sulfoethyl methacrylate and sulfopropyl acrylate; and phosphoric acids, such as 2-phosphoethyl (meth)acrylate and vinylphosphoric acid. Additional polymerizable, unsaturated monomers which can be used as carboxylate-free monomers include, for example, aromatic monomers such as styrene, alpha-methylstyrene and vinyltoluene; acrylonitriles, such as acrylonitrile itself, methacrylonitrile, alpha-chloroacrylonitrile and ethylacrylonitrile; vinyl ethers, such as methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-dimethylaminooctyl vinyl ether, 1,4-butaneglycol divinyl ether, diethylene glycol divinyl ether; allyl compounds, such as B. Allyl chloride, methallyl chloride, allyl methyl ether and allyl ethyl ether; other monomers, such as E.g. vinylidene chloride, vinyl chloride, vinyl fluoride, vinylidene fluoride, sodium vinyl sulfonate, butyl vinyl sulfonate, phenyl vinyl sulfone, methyl vinyl sulfone, N-vinylpyrrolidinone, N-vinyloxazolidinone, triallyl cyanurate, triallyl isocyanurate, acrolein, acrylamide, methacrylamide, allyltriethoxysilane, allyltris(trimethylsiloxy)silane and 3-acryloxypropyltrimethoxysilane.

Other carboxylate-free monomers may also be used, including monomers free of a carboxylate surfactant moiety and bearing Rc groups, including polymerizable allyl and vinyl functional carboxylate-free surfactant monomers. Ethyl acrylate is a preferred carboxylate-free monomer. Up to 30 wt.% of the first class polymer may be comprised of the polymerized moieties of a carboxylate-free monomer not containing Rc groups. A carboxylate-free monomer is represented by the group D in formula (I) and, in the case of an Rc functional carboxylate-free monomer, also in the groups C'. One or more carboxylate-free monomers may be copolymerized with the ethylenically unsaturated C3-C6 carboxylic acid monomer.

The polymers of the second structural class of the present invention are prepared by a process. In the first step of the process, a compound, preferably an alcohol, containing the surface-active radical Rc is used to esterify or transesterify a mercapto acid or mercapto ester by conventional methods. Preferably, the mercapto acids used have the formula HO₂C(CH₂)c-SH when c is 1, 2 or e is 3. Examples of mercapto acids that can be used include 3-mercaptopropionic acid, 4-mercapto-n-butyric acid and mercaptoacetic acid. Preferably, an alkyl ester of one of the preferred mercapto acids is used when the "surface-active" mercaptan is prepared by transesterification. Methyl 3-mercaptopropionate can be used, for example.

In the second step of the process for producing the polymers of the second class, a surface-active mercaptan is used as a chain transfer agent in an otherwise conventional polymerization of a ethylenically unsaturated C₃-C₆ monocarboxylic acid monomer and optionally a carboxylate-free monomer. For example, the mercaptan surfactant can be used as a chain transfer agent in solution polymerization in water, in a water-miscible solvent such as isopropanol, and in a mixture of water and a water-miscible solvent.

The detergent compositions of the present invention include at least one surfactant selected from anionic, nonionic and cationic surfactants. When preparing liquid detergent compositions, it is preferred that the water-soluble polymer and its concentration in the detergent composition be selected to be compatible with the other components of the composition. That is, addition of effective amounts of the water-soluble polymer should not induce phase separation and that the polymer should be soluble or dispersible in the composition at the concentration employed. Preferably, the liquid detergent compositions of the present invention contain from 0.5% to 5% by weight of the polymer.

Examples of classes of anionic surfactants which can be used in formulating detergent compositions of this invention are both soaps and synthetic anionic surfactants. Examples of soaps include the higher solid acid soaps such as the sodium and potassium salts of C10-C18 fatty acids which are derived from saponification of natural fats such as tallow, palm oil and coconut oil, or from petroleum, or which are prepared synthetically. Depending on the source, these fatty acid salts can have either an even or odd number of carbon atoms and can be branched or have straight carbon chains.

The anionic surfactants are, for example, water-soluble salts of sulfonated paraffin, which is derived from alkylbenzenes and is usually referred to in the art as linear alkylbenzenesulfonate surfactants (LAS); sulfonated fatty alcohols ("alcohol sulfates" - AS); sulfate ethers derived from nonionic surfactants ("alcohol ether sulfates" - AES); alpha-olefin sulfonates derived from oligomerized ethylene or alpha-olefins (AOS); secondary alkane sulfonates (SAS) derived from paraffins; alkoylamides prepared by ammonolysis of lower alkyl esters of fatty alcohols with alkanolamines; amine oxides derived from oxidation of amines prepared from fatty alcohols or alpha-olefins; Sulfosuccinates derived from fatty alcohols and maleic anhydride. Heavy duty liquid detergent products for laundry purposes often contain LAS and/or non-ionic surfactants. Light duty detergent products for dishwashing often contain LAS and AES or AES and amine oxide surfactants.

Examples of classes of nonionic surfactants which can be used in formulating detergent compositions of the present invention include condensation products of alkylene oxides and fatty alcohols such as those derived from coconut oil, tallow and tall oil; condensation products of alkylene oxide and alcohols derived from ethylene which has been oligomerized by the Ziegler process; condensation products of secondary alcohols derived from paraffin; condensation products of alkylphenols and alkylene oxides.

In addition to one or more surfactants and the water-soluble polymer, the detergent composition may also contain, for example: additional builders, such as sodium tripolyphosphate (solid compositions) or tetrapotassium pyrophosphate (liquid compositions), sodium carbonate, sodium citrate and zeolites; preservatives, such as sodium silicate; additional redeposition preventers, such as carboxymethylcellulose and polyvinylpyrrolidone; dyes; perfumes; foam stabilizers, such as amine oxides; enzymes, such as proteases, amylases, cellulases and lipases; fabric softeners; processing aids, such as sodium sulfate; bleaching agents, e.g. chlorine and oxygen bleaches; optical brighteners; antistatic agents; hydrotopes, such as B. Xylene and toluene sulfonate and ethanol; opaque agents; and skin protection agents (liquid light detergents).

The polymers of the present invention can be advantageously used to replace a portion of the phosphate builder in certain detergent compositions, thereby reducing the adverse effect of waste water containing the detergent in the environment.

The water-soluble polymers of the present invention are of particular value as additives to commercial heavy-duty liquid detergent compositions and light-duty consumer detergent compositions. These products are highly formulated materials containing a relatively large number of components. Despite the large number of possible adverse interactions between one or more of the existing components of these commercial products and the water-soluble polymer, the polymer can be added directly without reformulating the detergent composition. This compatibility is very advantageous and allows detergent manufacturers to quickly realize the benefits of the present invention.

In addition to serving as builders and detergent aids in liquid detergent compositions for consumer laundry and dishwashing purposes, the polymers of the present invention can also be used in other cleaning products as well as dispersants in a variety of applications. For example, the polymers can be used as ingredients in cleaning compositions formulated for use as consumer and institutional hard surface cleaners, in solid detergent and soap compositions such as bars, cakes, tablets and powders, in institutional and industrial cleaning products, in the food and food service industries and in commercial and institutional laundries, in metal degreasing compositions, in wallpaper cleaners and in automotive cleaning products.

Formulations for a variety of detergent products can be found, for example, in Detergency, Part I, (W. G. Cutler and R. C. Davis eds., Marcel Dekker, New York, 1972) at 13-27.

As dispersants, the polymers are used as pigment dispersants for coatings, paints and varnishes, and as particle dispersants for borehole muds and coal slurries.

The polymers of this invention are also useful in water treatment and particularly in products and applications that employ sequestering agents for hard water ions.

The present invention will now be illustrated by means of the following examples, which are intended for illustrative purposes only and are not to be considered as limiting the scope of the invention in any way.

In the following examples, the percentage of a composition is given by weight.

The following abbreviations are used in the examples that follow:

IPA Isopropanol

MAc Maleic acid

MAn Maleic anhydride

AA Acrylic acid

MAA Methacrylic acid

Lup 11 Lupersol (trademark of Pennvalt Corp.) 11, tert.butyl peroxypivalate (75% w/w in mineral spirits)

EO Ethylene oxide

TGA Tioglycolic acid (95%)

DDM n-dodecyl mercaptan

NaPS sodium persulfate

EA Ethyl Acrylate

3-MPA 3-mercaptopropionic acid

example 1 Preparation of a copolymer in a hydrophilic solvent

In a reactor equipped with a stirrer, 750 parts by weight of deionized water and 250 parts of isopropanol were heated to 82°C. A monomer/initiator mixture was prepared containing 350 parts by weight of acrylic acid, 150 parts by weight of an ester of methacrylic acid and a (C16-C18)alkoxypoly(ethyleneoxy)ethanol containing about twenty ethoxy units, and 8 parts by weight of methacrylic acid. Five minutes before the monomer/initiator feed began, 2 parts by weight of Lupersol 11 was added to the isopropanol mixture at 82°C. The monomer/initiator mixture was then metered over 2 hours while maintaining the reactor contents at 82°C. Thereafter, the reactor contents were heated to 82°C for an additional 30 minutes, then cooled to obtain a copolymer dissolved in a water/isopropanol mixed solvent.

Examples 2-27 and comparative examples 1-2

The procedure of Example 1 was repeated using the weight proportions of the components shown in Table I to prepare the water-soluble copolymers of Examples 2-27 and Comparative Examples 1 and 2. In preparing their Comparative Examples copolymers, maleic acid was included in the initial batch in the amount shown in the table. TABLE I Initial Batch Monomer/Initiator Feed Example Parts Esters of MAA and EO Alcohol Type EO Alcohol Comparative Example

1. Indicates the number of carbon atoms in the alkyl group and the degree of ethylene oxide polymerization in the alkyloxypoly(ethyleneoxy)ethanols.

2. Administered during the first 1.33 hours as a solution in 260 parts isopropanol.

Example 28 Production of copolymers in water

In a reactor equipped with a stirrer, 666.5 parts by weight of deionized water and 31.2 parts of sodium dodecylbenzenesulfonate were heated to 92°C. A mixture of 40 parts of deionized water and 12.9 parts of thioglycolic acid was metered over 2 1/2 hours, maintaining the reactor contents at 92°C. A mixture of 140 parts of acrylic acid, 60 parts of an ester of methacrylic acid and (C16-C18)alkyloxy(ethyleneoxy)19-ethanol, and 78 parts of Lupersol 11 were metered over 3 hours, maintaining the reactor contents at 92°C. Thereafter, the mixture was heated to 92°C for an additional 30 minutes. Then a mixture of 356 parts deionized water and 18.6 parts 50% sodium hydroxide was added while maintaining the reactor contents at 92°C. Thereafter the reactor contents were cooled to 83°C and 18.9 parts 30% hydrogen peroxide were added. Then the reactor contents were cooled to room temperature.

Examples 29-31

The procedure of Example 28 was used to prepare the water-soluble polymers of Examples 29-31 using the components listed in Table II. In the case of Example 29, an initiator mixture consisting of 40 parts water and 8 parts sodium persulfate was metered into the reactor flask simultaneously with the mercaptan mixture. Table II Example initial batch Mercaptan mixture Initiator mixture Monomer mixture Example Ester(II) parts

1. Esters of methacrylic acid with (C₁₆₋₁₈)alkoxy(ethyleneoxy)₁₉-ethanol.

Example 32

In a reactor equipped with a stirrer and a reflux receiver, 72 parts by weight of toluene and 233 parts by weight of Macol (trademark of Mazer Chemicals) CSA 20, which is a (C₁₆-C₁₈)alkoxy(ethyleneoxy)₁₉-ethanol, were heated to reflux until all water was removed. Thereafter, a mixture of 100 parts of acrylic acid and 2 parts by weight of di-tert-butyl peroxide initiator and a mixture of 19 parts of toluene and 10.5 parts of 3-mercaptopropionic acid were metered in over 2 hours while the reactor contents were kept at reflux. Toluene was, removed as needed to maintain the reflux temperature at about 140°C. After polymerization was complete, the reaction mixture was maintained at reflux until esterification was complete. The extent of esterification was monitored by the amount of water removed. The reaction mixture was then heated under vacuum until all of the toluene was removed. The resulting copolymer was recovered from the reactor mixture as 100% solids.

Example 33

The procedure of Example 32 was repeated except that an initial charge of 22 parts toluene was present in the reactor, tert-butyl peroctoate was used as the initiator, and 20 parts 3-mercaptopropionic acid was used as the chain transfer agent (no toluene).

Example 34 Preparation of a copolymer containing an acrylic acid/urethane monomer

In a reactor equipped with a stirrer, 600 parts by weight of isopropanol was heated to 82°C. A monomer/initiator mixture was prepared containing 210 parts of acrylic acid, 90 parts of a urethane of α,α-dimethyl-meta-isopropylbenzyl isocyanate and a (C16-C1)alkoxy(ethyleneoxy)19-ethanol, and 4.8 parts of Lupersol 11. Five minutes before the monomer/initiator feed began, 1.2 parts of Lupersol 11 were added to the isopropanol at 82°C. The monomer/initiator mixture was then metered for 2 hours while maintaining the reactor contents at 82°C. The reactor contents were then heated to 82°C for an additional 30 minutes and then cooled.

Example 35 Preparation of a copolymer terminated with a surface-active residue

In a reactor equipped with a stirrer, 220 parts of deionized water and 240 parts of tert-butanol were heated to reflux. A mixture of 252.2 parts of acrylic acid and 98.2 parts of a thiol-terminated ester of 3-mercaptopropionic acid and a (C16-C18)alkoxy-(ethyleneoxy)19-ethanol, and a mixture of 20 parts of deionized water, 50 parts of tert-butanol and 5.05 parts of Lupersol 11 initiator were metered separately over 3 hours while maintaining the reactor contents at reflux or at 85°C, whichever was lower. Thereafter, the reactor contents were heated to reflux or at 85°C, whichever was lower, for an additional 30 minutes and then cooled.

Comparison example 3 Preparation of a maleic acid-containing copolymer

A maleic acid-containing copolymer was prepared as a comparative example as disclosed in U.S. Patent 4,559,159. In a reactor equipped with a stirrer, 176.3 parts of maleic anhydride and 206.5 parts of deionized water were heated to 75°C. Then 259 parts of 50% sodium hydroxide were added and the reactor contents were then heated to 100°C. A mixture of 299 A mixture of 185 parts of deionized water, 208.7 parts of acrylic acid and 46.4 parts of an ester of methacrylic acid and a (C16-C18)alkoxy(ethyleneoxy)19-ethanol was metered over 5 hours while maintaining the reactor contents at 100°C. A mixture of 185 parts of deionized water, 4.7 parts of sodium persulfate and 15.5 parts of 30% hydrogen peroxide was metered over 6 hours while maintaining the reactor contents at 100°C. Thereafter, the reactor contents were heated to 100°C for an additional 2 hours. The mixture was then cooled and further neutralized with 308.7 parts of triethanolamine. The resulting water-soluble polymer was found to have a weight average molecular weight of 22,000 by gel permeation chromatography.

Comparative examples 4 and 5 Preparation of a copolymer of acrylic acid and half-esters of polyethylene glycol and methacrylic acid

In a reactor equipped with a stirrer, 200 parts of isopropanol were heated to 82°C. A monomer/initiator mixture was prepared containing 70 parts of acrylic acid, 30 parts of a half-ester (prepared according to the procedure described in U.S. Patent 3,719,647) of methacrylic acid and polyethylene glycol (average molecular weight 3400 - Comparative Example 4, average molecular weight 1000 - Comparative Example 5), and 1.6 parts of Lupersol 11 initiator. Five minutes before the monomer/initiator feed began, 0.4 parts of Lupersol 11 initiator were added to the isopropanol at 82°C. The monomer/initiator mixture was then metered for 2 hours while maintaining the reactor contents at 82°C. The reactor contents were then heated to 82ºC for a further 30 minutes and then cooled.

Example A - Lime soap dispersibility

Using the method given in JAOCS 21 (1950) 88, the lime soap dispersibility of water-soluble copolymers of the present invention was measured and compared with that of acrylic acid homopolymers (Comparative Examples 6-8) and copolymers of acrylic acid and half-esters of polyethylene glycol and methacrylic acid (US Patent 3,719,647 - Comparative Examples 4 and 5). The results given in Table III indicate that the copolymers of the present invention are superior to both the acrylic acid homopolymers and the copolymers of US Patent 3,719,647 in lime soap dispersibility, which is an important requirement for detergent compositions used in hard water washing. TABLE III Example or Polymer Composition Comparative Example Molecular Weight of Polymer Lime Soap Dispersibility Comp. Example E.g.

1. Comparative Examples 6-8 are acrylate homopolymers prepared by a standard aqueous process employing chain transfer agents to provide a low molecular weight polymer.

2. The indexing indicates the number of ethylene oxide units in the poly(ethyleneoxy)ethanol segment and the number of carbon atoms in the alkyl segment of the ester.

3. Determined by gel permeation chromatography.

Example B - Anti-dirt deposit

Using the protocol set forth in ASTM Method D 4008-81, the antisoil deposit properties of water-soluble copolymers of the present invention were evaluated in comparison with prior art polymers, including homopolymers of acrylic acid and copolymers containing maleic acid. 50 g of polymer solution (0.080% w/w), followed by a 50 g rinse of the polymer solution vessel with deionized water, were added to the pots of a Terg-O-Tometer for each test. Antisoil deposit was measured using a bleached 100% cotton fabric, 50/50 polyester-cotton blend fabric and 100% cotton Oxford broadcloth fabric were used. The results of these measurements are reported in Tables IV and V. The results clearly demonstrate that the copolymers of the present invention help prevent soil deposits from dirty water and that they are particularly effective in helping prevent soil deposits on a cotton/polyester fabric. Furthermore, surprisingly, their antisoil deposit characteristics are comparable to or superior to those of copolymers containing maleic acid. TABLE IV Example or Comparative Polymer Composition Polymer Molecular Weight %Antisoil Deposition (3 Cycles) Reflectivity on Cotton (Avg.) % Reflectivity on PE : Cotton (Avg.) Comp. Ex. Ex.

1. % reflectance on bleached 100% cotton fabric, average of 20 determinations (10 fabrics, two sides).

2. % reflectance on 65/35 polyester/cotton fabric, average of 20 tests (10 fabrics, two sides). Table V Example or comparative example Polymer composition Polymer molecular weight %Anti-soil deposition (3 cycles) Reflectivity on cotton (avg.) % Reflectivity on PE : Cotton (avg.) Comp. example Ex.

1. % reflectivity on 100% cotton bleached wide oxford fabric. 2. % reflectivity on 65/35 cotton/polyester fabric.

Example C - Anti-deposit with a liquid detergent

The soil antideposit test was repeated using the protocol of ASTM Method D 4008-81, except that 50 g of a commercial detergent solution (4.0% w/w) and 50 g of the polymer solution (0.080% w/w) were added to the Terg-O-Meter test pots for each test. The results of the tests are reported in Tables VI and VII and demonstrate that the water-soluble polymers of the present invention improve the soil antideposit properties of commercially available liquid household laundry detergents. In addition, the improvement is unexpectedly greater than that obtained using either a homopolymer of acrylic acid (Comparative Example 6), polyethylene glycol, additional anionic or nonionic surfactants, or alkoxypolyethoxyethanol. TABLE VI Example or Comparative Polymer Composition Polymer Molecular Weight Detergent %Antisoil Deposition (3 Cycles) % Reflectivity on Cotton (Avg.) % Reflectivity on PE : Cotton (Avg.) Comp. Ex. Ex.

1. Bleached fabric made of 100% cotton.

2. 65/35 polyester/cotton blend.

3. Sodium carboxymethylcellulose.

4. Commercial Detergent A is a liquid household detergent which contains: "detergents (anionic, nonionic and cationic surfactants, enzymes), water softeners (laurate, citrate), dispensing aids (ethyl alcohol, propylene glycol), buffering agents, water, stabilizing agents, soil suspending agents, fabric whitening agents, colorants and fragrances". Table VII Example or Comparison Polymer Composition Polymer Molecular Weight Detergent % Antisoil Deposit (3 Cycles) % Reflectivity on Cotton (Avg.) % Reflectivity on PE : Cotton (Avg.) No Polymer Ex.

1. Wide oxford fabric made of 100% cotton.

2. 65/35 polyester/cotton blend.

3. Macol (trademark of Mazer Chemicals) CSA-20 (C₁₆-C₁₈)Alkoxy(ethoxy)₁₉-ethanol.

4. Neodol (trademark of Shell Chemical Co.) 25-7 - (C₁₂-C₁₅)alkoxy(ethoxy)₆-ethanol non-ionic surfactant.

5. Carbowax (trademark of Union Carbide Corp. 8000 - polyethylene glycol).

6. Sodium lauryl sulfate - anionic surfactant.

7. See above Table VI.

8. Commercial Detergent A is a liquid household detergent which contains "a combination of anionic and nonionic surfactants (wetting agents to loosen soil); sodium citrate (softens water, improves cleaning); stabilizer (prevents product separation); buffering agent (improves cleaning), soap (suds controller), fragrance, brightener and colorant".

9. Commercial Detergent B is a liquid household detergent for washing which is "an aqueous suspension containing: a combination of anionic and nonionic surfactants (wetting agents to loosen soil); sodium citrate (softens water, improves cleaning); stabilizer (prevents product separation); buffering agent (improves cleaning); anti-redeposition agent (suspends soil); perfume, brightener, opacifier and colorant".

Example D - Compatibility with liquid household detergents

The polymers were added to a commercial detergent A and a commercial detergent B, the compositions of which were referred to above. The initial level of polymer was 1%, which was increased if compatibility was found.

The detergent/polymer solutions were stored at room temperature and evaluated for stability (phase separation) over a period of approximately 270 days if initially stable.

As shown in Table VIII, the polymers of the present invention were more compatible in the high surfactant liquid laundry detergents than the acrylic acid homopolymer. TABLE VIII Commercial Detergent Polymer Level Observation Comp. Ex. 6 Phase separation - 7 hours stable Phase separation - 24 hours Phase separation - immediately stable

Example E - Foam stability of detergents for hand dishwashing

The effect of adding water-soluble polymers of the present invention on the foam stability of hand dishwashing detergents was measured using the procedure of R. M. Anstett and E. J. Schuck, J.A.O.C.S. (Journal of the American Oil Chemists Society) (October 1966), Volume 43, pages 576-580.

The results reported in Table IX indicate that the water soluble polymers of the present invention enhance the cleaning performance of hand dishwashing detergents as measured by foam stability. It should be noted that the addition of the polymer increases solids by about 13%, but performance with polymer addition increases by about 50%. TABLE IX Polymer Example Plate Units Total Plate No Polymer

1. The polymer was used at a level of 5% by weight of detergent, which detergent was a commercial product containing biodegradable surfactants and no phosphorus and had 39.3% solids.

Example F - Cleaning of hard surfaces - machine dishwashing

The effect of copolymers of the present invention on the performance of machine dishwashing detergents was studied using a modification of ASTM Test Method D 3556-85, "Deposition on Glassware during Mechanical Dishwashing." The modifications to the test method were a higher soil load, 60 g instead of the 40 g specified in the method, and washing the dishes using a "short" dishwashing cycle. This provides for a 25 minute wash, a 2 minute rinse, and an 8 minute rinse. The test conditions were: 54°C, 200 ppm hardness as CaCO3 (hard water), and 37.5 g of liquid detergent (Cascade

- trademark of Proctor and Gamble). The polymer used was similar to Example 32, having a composition of about 30% acrylic acid and 70% of a cetyl/stearyl alcohol with 40 moles of ethylene oxide and a Mn of about 3700. This was used at a level of 2% based on the detergent.

The results after one cycle shown in Table X demonstrate the advantage of the polymer of the present invention in the detergent with the glass rating in staining. The rating system is similar to the test procedure: 0 - no staining, 1 - staining barely noticeable, 2 - slight staining, 3 - 50% of the glass is covered with stains, and 4 - the entire glass is covered with stains. Table X Staining on glass Grease deposits Detergent Cascade with 5% added polymer Staining on glass

Example G - Powdered washing detergents Inhibition of crust formation

These tests were conducted under European washing conditions using a Launder-O-Meter which simulates a European type machine. The device is described in U.S. Patent 4,559,159. The test conditions were: 60ºC, 430 ppm hardness as CaCO₃, detergent concentrations of 1% and 0.6%. Four percent polymer was added to the detergent, which detergent also contained 8% linear alkyl lauryl sulfonate, 4% sodium oleate, 20% tetrasodium pyrophosphate, 5% sodium silicate (2.4:1), 5% sodium carbonate, 20% sodium sulfate, 0.5% sodium carboxymethylcellulose and the balance water.

Cotton terry cloth samples were washed in the Launder-O-Meter for 10 cycles. One cycle consisted of a 20 minute soak, a 20 minute wash and 2 5 minute rinses. The samples weighed approximately 25 g and were washed in 100 g of wash solution to give a 4:1 water to fabric weight ratio. The fabric was then ashed at 800ºC for five hours and the scaling was measured.

The results presented in Table XI indicate that the polymer of the present invention is more effective in inhibiting scale formation than an acrylic acid homopolymer. TABLE XI Polymer Composition Residual ash values Ash None Comparison Example 6 Example 4

Example H - Inhibition of calcium carbonate

Using the procedure described in US-A4,326,980, the inhibition of calcium carbonate formation by the polymers of the present invention was measured. The results given in Table XII show that the polymers of the present invention are effective in inhibiting effective in the formation of calcium carbonate, which is a useful property in both detergent and water treatment applications. TABLE XII Example or Comparative Polymer Polymer Composition Molecular Weight % Inhibition Comp. Ex. Ex.

1. Belclene (brand of Ciba-Geigy) 200 - polymaleic acid.

2. Dequest (brand of Monsanto) 2000 - Aminotri(methylenephosphonic acid).

Example I - Dispersion of a kaolin clay

The ability of the polymers of the present invention to disperse kaolin clay in an aqueous medium was measured as follows. 430 mL of 200 ppm CaCO3 (Ca:Mg/2:1, as CaCO3) and 0.43 g of Hydrite (brand of Corgia Kaolin) UF Kaolin (1000 ppm kaolin) were placed in a multimix jar and mixed on a multimixer for 10 minutes. The pH of the mixture was adjusted to 7.5 with dilute NaOH. Then 100 mL aliquots of the mixture were added to 4 ounce jars, shaking the mixture in the sample jar after pouring in each other aliquot. 5, 10, and 20 ppm polymer (0.5, 1, 2 mL of a 0.1% solution, adjusted to pH 8.0) were added to each of three aliquots of the kaolin/CaCO3 mixture. The vials were shaken at low speed for 15 minutes in a mechanical shaker. After the vials were removed from the shaker, they were allowed to rest on a rest bench for 2 hours. Without disturbing the vials, the top 20 mL was removed and each sample was placed in its own 28.35 g (1 ounce) vial. The turbidity of each solution in the vials (0-1000 NTU) was read using a Fisher Turbidimeter Model DRT 100B.

The results presented in Table XIII demonstrate that the polymers of the present invention can effectively disperse kaolin clay. TABLE XIII Example Polymer Composition Turbidity No Polymer Comp. Ex. 6 Ex.

Example J - Inhibition of the formation of barium sulfate

The effectiveness of the polymers of the present invention in inhibiting the formation of barium sulfate was evaluated using the following procedure:

The following solutions were prepared

Formation water Sea water*

74.178/1 NaCl 23.955 g/l NaCl

10.31 g/l CaCl₂·2 H₂O 1.57 g/l CaCl₂·2 H₂O

4.213 g/l MgCl₂·6 H₂O 11.4362 g/l MgCl₂·6 H₂O

0.7098/1 KCl 0.8771 g/l KCl

1.747 g/l SrCl₂·6 H₂O 0.0243 g/l SrCi₂·6 H₂O

0.448 g/l BaCl₂·2 H₂O 4.3769 g/l Na₂SO₄

0.0170 g/Na₂SO₄ 0.1707 g/l NaHCO3

0.638 g/l NaHCO3

* Filtered through a 0.45 µm filter.

The pH of the formation water and sea water was adjusted to pH 6 by bubbling nitrogen (to raise the pH) or carbon dioxide (to lower the pH) through the solutions. The pH of another sample was adjusted to 4 with carbon dioxide and with concentrated HCl. For each test sample, the following compounds were added to a 113.4 g (4 ounce) clear jar:

1. Polymer dose (1.3 ml of a 0.1% polymer solution at pH 6) (3.9 ml of a 0.1% polymer solution at pH 4)

2. 50 ml sea water (mix)

3. 50 ml formation water (mix).

The samples were placed in an oven at 90ºC for 15 hours and then filtered while still hot through a 0.45 µm filter. The filtered samples were analyzed for Ca by EDTA titration and for Ba and Sr by atomic absorption. The percent inhibition was calculated as follows.

% Inhibition = (M) sample-(M) empty/(M) 100% Inhibition-(M) empty · 100 Ion dilution total 100 ml

100% inhibition (calculated):

Ba 126 ppm Ba = 214 ppm as BaSO₄

291 ppm Sr

Ca 4043 ppm Ca as CaCO₃.

The results reported in Table XIV demonstrate that the copolymers of the present invention are effective in preventing the formation of barium sulfate under the conditions encountered in oil wells. It is believed that the polymers of the present invention are particularly useful in flooding oil fields with carbon dioxide and in other applications where the pH is low (e.g., about 4) for oil recovery. It is also believed that the polymers of the present invention are useful in redispersing barium sulfate in oil wells which are plugged with a "stone" containing barium sulfate. TABLE XIV Example Polymer Composition Polymer Molecular Weight % BaSO4 Inhibition No Polymer Comp. Ex. Ex. 20Ex. Comp. Ex. Poly(phosphinoacrylic acid polystyrene sulfate

1. Acrylic acid/methacrylic acid copolymer.

2. Dequest (brand of Monsanto) 2060 - Diethylenetriaminepentamethylenephosphonic acid.

3. Belsperse (brand of Ciba-Geigy) 161 - Poly(phosphinoacrylic acid)

4. Versa (brand of National Starch) TL-77 – Polystyrene sulfonate.

Example K - Coal dispersibility

The effectiveness of the polymers of the present invention in dispersing coal to form a 70% slurry was measured according to the following procedure.

200 g of Pittman Moss #1 carbon was weighed and 85.7 g of dispersant (2% or 3% solution, depending on the desired concentration of dispersing solids) plus 3 g of deionized water was added directly into a one-quart stainless steel Multimixer mixing cup. The carbon was transferred to the cup and mixed by hand with a large stainless steel spatula until all of the carbon was wetted. The mixture was mixed using a Multimeter (brand of Sterling Multi-Products, Inc.) mixer in a cap. Initially, the mixture was agitated by hand. The cup was agitated slowly while the ON button was activated so that the mixture flowed uniformly. Then the cup was placed in position and the contents were mixed for 20 minutes. Progress was checked every 5 minutes and the mixture was mixed by hand when necessary. After mixing, the temperature was immediately and quickly measured with a Brookfield RVT viscometer at 10, 20, 100, 20, 10 rpm using shaft #5.

The results presented in Table XV demonstrate that the polymers of the present invention were more effective at dispersing coal to form a 70% slurry than a naphthalene sulfonate dispersant or an acrylic acid homopolymer. TABLE XV Example or Comp. Example Additive Composition Level (on carbon) Viscosity Comp. Example 6 Naphthalene Sulphonate Failure - Not liquid

1. Measured using a Brookfield RVT viscometer equipped with a No. 5 shaft and reported as a function of shaft angular velocity. Viscosity is given in cps (1 cps = 1 x 10-3 Pa s).

Example L - Enzyme stability

Commercial heavy-duty detergent compositions may contain a protease to aid in cleaning by digesting protein stains. The compatibility of the polymers of the present invention with proteases used in detergent compositions was evaluated using a procedure recommended by the enzyme supplier Novo Enzyme Co., given in L. Kravetz et al, J.A.O.C.S., 62 (1985) 943-949.

To determine the proteolytic activity of alkaline proteases, a protease was allowed to hydrolyze azocasein for 30 minutes at 40ºC. Undigested protein was precipitated with trichloroacetic acid and the amount of digested product was determined by spectrophotometry.

Using this method, the enzymatic activity of some proteases in a commercial heavy-duty liquid detergent composition containing a water-soluble polymer of the present invention was measured as a function of time and compared with similar data from control detergents.

The results presented in Table XVI demonstrate that the polymers of the present invention are compatible with liquid detergent compositions containing proteases and do not inhibit their enzymatic activity. TABLE XVI Relative Activity (Mean of Duplicates) Additive Initial Alkalase + 1.5% Example 21 Savinase + 1.5% Example 21 Esperase + 1.5% Example 21

1. Detergent: Commercial detergent Tide (Procter and Gamble brand) (neat) with 0.6% enzymes added. Enzymes supplied by NOVO Industries. Test solutions stored at room temperature.

Claims (17)

1. Water-soluble polymer selected from (a) water-soluble polymers represented by the general formula: A (B)m ( )n(D)o E, where (1) A is selected from a group of Rb-C(O)-Ra- and Rc-C(O) NH-Rd-; Ra is selected from (C₁-C₅)alkylidene and (C₁-C₅)alkylidene derivatives including a chain initiator or a chain transfer radical; Rb is selected from -OQ and Rc; Rc has the formula R¹ Z (X¹)a (X²)b R¹ is selected from (C₁-C₁₈)alkyl, alkaryl in which the alkyl moiety contains 1 to 18 carbon atoms and aralkyl in which the alkyl moiety contains 1 to 18 carbon atoms; Z is selected from -O-, -S-, -CO₂-, -CONR²- and -NR²- X¹ is -CH₂CH₂O-; X² is -C(CH₃)HCH₂O-; a is a positive integer and b is 0 or a positive integer where the sum of a and b is 3 to 100, and it should be understood that X¹ and X² units may be arranged in any sequence; R² is selected from H, (C₁-C₄)alkyl and H(X¹)d(X²)e-; d and e independently of one another are 0 or a positive integer, the sum of d and e being from 1 to 100; Q is selected from H and the positive ions form soluble salts with carboxylate anions; Rd is a group including a carbon-carbon single bond formed from a polymerizable carbon-carbon double bond during polymerization of the polymer; wherein (2) each B is a group with the formula -Re-C(O)-OQ, Re is a saturated trivalent aliphatic group having 2 to 5 carbon atoms; where (3) each group is selected from -Re-Rc, -Rf-NHc(O)-Rc and Re-C(O)-Rc, Rf is a group including a carbon-carbon single bond formed from a polymerizable carbon-carbon double bond during polymerization of the polymer; where (4) each D is a group having the formula -Re-G, where G is an organic group excluding Rc and -CO₂Q; where (5) E is a group selected from Rc-Rg-, Rb-C(O)-Rg- and Rc-C(O)NH-Rd, where Rg is selected from (C1-C5)alkylene and (C1-C5)alkylene derivatives including a chain initiator or chain transfer radical; in is a positive integer and n or o are independently 0 or a positive integer, n is selected such that (B)m comprises from 20 to 95% by weight of the polymer, n is selected such that Rc comprises from 80 to 4% by weight of the polymer, o is selected such that (D)o comprises from zero to 30% by weight of the polymer, wherein the sum of the weight percentages of A, (B)m, ( )n, (D)o and E is 100% and it should be further understood that the B and D groups can be arranged in any sequence; and the polymer has a number average molecular weight of 500 to 50,000; and (b) water-soluble polymers having the formula L-J , where L- has the formula Rc-C(O) (CHR³)c-S, -J has the formula -(B)m(D)oE, where the index c is selected from 1, 2 and 3, R³ is selected from H-, CH₃- and C₂H₅-, and the weight ratio of L to J is from 1:340 to 7:1, o is a positive integer and is selected such that (D)o comprises up to 40% by weight of the polymer, the sum of m and o is 10 to 500 and Rc, B, D, E and m are as defined above. 2. Water-soluble polymer according to claim 1, wherein (a) Ra, if present, is selected from (C₂-C₅)alkylidene and (C₂-C₅)alkylidene derivatives including a chain initiator or chain transfer radical; and/or (b) Rg, if present, is selected from (C₂-C₅)alkylene and (C₂-C₅)alkylene derivatives including a chain initiator or chain transfer radical; and/or (c) R¹, when present, is selected from (C₁-C₁₈)alkyl, (C₇-C₁₈)alkaryl and (C₇-C₁₈)aralkyl. 3. A water-soluble polymer according to claim 1 or 2, wherein: (1) A is selected from (2) B is a group with the formula (3) C is a group with the formula (4) E is selected from -CH₂-CH₂-C(O)-OQ and -CH₂CHCH₃-C(O)-Rc. 4. A water-soluble polymer according to claim 3, wherein the polymer includes Rc groups having the formula R¹O(X¹)a-, where R¹ is (C₁-C₁₈alkyl and a is 5 to 45. 5. A water-soluble polymer according to claim 4, wherein R¹ is (C₁₀-C₁₈)alkyl. 6. A water-soluble polymer according to claim 1 or 2, which has the formula L-J wherein the sum of m and o is 20 to 150. 7. A water-soluble polymer according to claim 1, 2 or 6 which has the formula L-J, wherein the weight ratio of L to J is 1:100 to 2:1. 8. A water-soluble polymer according to any one of the preceding claims, wherein G is selected from -NH₂, -NHR₃, -OR₃, -OR⁴-OH, -OR⁴-NH, -OR⁴-SO₃Q, -OR⁴-PO₃Q₁, R⁴ is (C₁-C₈)alkyl and R⁴ is (C₁-C₈)alkylene. 9. A water-soluble polymer according to any one of the preceding claims, wherein Rd is alpha,alpha-dimethyl-meta-isopropenylbenzyl. 10. A water-soluble polymer according to any one of the preceding claims, wherein the number average molecular weight of the polymer is 1000 to 15,000, preferably 1000 to 5000. 11. Water-soluble polymer represented by the general formula L-J, wherein (a) L has the formula Rc-C(O)(CHR³)c-S; RC has the formula R¹ Z (X¹)a (X²)b; R¹ is selected from (C₁-C₁₈)alkyl, alkaryl in which the alkyl moiety contains 1 to 18 carbon atoms, and aralkyl in which the alkyl moiety contains 1 to 18 carbon atoms; Z is selected from -O-, -S-, -CO₂-, -CONR²- and -NR²- X¹ is -CH₂CH₂O-; X² is -C(CH₃)HCH₂O-; a is a positive integer and b is 0 or a positive integer where the sum of a and b is 3 to 100, and it is to be understood that X¹ and X² units may be arranged in any sequence; R² is selected from H, (C₁-C₄)alkyl, and H(X¹)a(X²)b-; c is selected from 1, 2 and 3; and R³ is selected from H-, CH₃ and C₂H₅-; (b) J has the formula -(B)m (D)o E, where (1) B the formula has, Re is a saturated trivalent aliphatic radical having 2 to 5 carbon atoms, Q is selected from H and the positive ions that form soluble salts with carboxylate anions; (2) D is, where G is an organic group excluding -CO₂Q; (3) E is a group selected from Rb-C(O)-Rg and Rc-C(O)NH-Rd-, Rg is (C2-C5)alkylene; m is a positive integer and o is 0 or a positive integer it being understood that the B and D groups may be arranged in any sequence, o is selected so that (D)o comprises up to 40% by weight of the polymer, and the sum of m and o is 10 to 500. 12. A polymer produced by a polymerization process comprising (1) Preparation of a mercaptan with the formula R¹ Z (X¹)a (X²)b - C(O) (CHR³)c-SH, wherein R¹ is selected from (C₁-C₁₈)alkyl, alkaryl in which the alkyl moiety contains 1 to 18 carbon atoms, and aralkyl in which the alkyl moiety contains 1 to 18 carbon atoms; R³ is selected from H-, CH₃- and C₂H₅-; Z is selected from -O-, -S-, -CO₂-, -CONR²- and -NR²-; X¹ is -CH₂-CH₂O-; and X² is -C(CH₃)HCH₂O-; a is a positive integer and b is 0 or a positive integer where the sum of a and b is 3 to 100, and it is to be understood that X¹ and X² units may be arranged in any sequence; and c is 1, 2 or 3; and (2) Using the mercaptan as a chain transfer agent in a subsequent polymerization of ethylenically unsaturated monomers including at least one ethylenically unsaturated carboxylic acid having 3-6 carbon atoms. 13. A detergent composition comprising a water-soluble polymer as claimed in any preceding claim, and a surfactant selected from anionic, nonionic and cationic surfactants and mixtures thereof. 14. A detergent composition according to claim 13, wherein the composition is liquid. 15. A detergent composition according to claim 13 or 14, wherein the detergent ingredients are selected to provide: (i) a heavy-duty detergent composition adapted to the washing of textiles; (ii) a light-duty detergent composition adapted to hand dishwashing; or (iii) a liquid composition adapted for machine dishwashing. 16. A method for cleaning textiles or for cleaning hard surfaces, which comprises washing the textile fabric or an article having the hard surface with a detergent composition according to any one of claims 13 to 15. 17. A method of improving the yield of a petroleum-containing geological formation by water injection techniques, the method comprising including in the flooding composition an effective amount of a water-soluble polymer to prevent the formation of barium sulfate, the water-soluble polymer being as defined in any one of claims 1 to 12.